CN105764980A - Surface treatment agent - Google Patents

Abstract

The present invention provides a surface treatment agent that does not use a fluorine-containing monomer, especially a fluorinated alkyl-containing monomer. The surface treatment agent is a water-based emulsion, containing: (1) non-fluoropolymer, which has a formula derived from (i): CH ₂ =CA ¹¹ -C(=O)-OA ¹² [wherein, A ¹¹ is A hydrogen atom or a methyl group, A ¹² is a straight-chain or branched aliphatic hydrocarbon group with 18 to 30 carbon atoms] The repeating unit of the long-chain (meth)acrylate monomer represented by (ii) having a ring (2) a surfactant containing one or both of a nonionic surfactant and a cationic surfactant; and (3) an aqueous liquid medium .

Description

surface treatment agent

technical field

The present invention relates to surface treatment agents, especially water and oil repellents and antifouling agents.

Background technique

Fluorine-containing water and oil repellent agents containing fluorine-containing compounds are currently known. The water and oil repellent agent exhibits good water and oil repellency when treating substrates such as fiber products.

According to recent research results [EPA report "PRELIMINARYRISKASSESSMENTOFTHEDEVELOPMENTALTOXICITYASSOCIATEDWITHEXPOSURETOPERFLUOROOCTANOICACIDANDITSSALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)], as a long-chain fluoroalkyl compound, PFOA (perfluorooctanoic acid: perfluorooctanoic acid) Concerns about environmental load gradually became clear. On April 14, 2003, the EPA (US Environmental Protection Agency) issued an intensified scientific investigation on PFOA.

On the other hand, Federal Register (FRVol.68, No.73/April16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf), EPA Environmental News FORRELEASE: MONDAYAPRIL14, 2003EPAINTENSIFIESSCIENTIFICINVESTIGATIONOFACHEMICAL( telomers by breakdown or metabolism It is possible to generate PFOA (the so-called telomer refers to long-chain fluoroalkyl). In addition, it has also been announced that telomers can be used in various products such as fire extinguishing foams, care products, cleaning products, carpets, textiles, paper, and leather imparted with water and oil repellency and antifouling properties. The accumulation of fluorinated compounds in the environment is a concern.

In addition, fluorine-containing water and oil repellent agents containing fluorine-containing polymers must be heat-treated at high temperatures (for example, 100° C. or higher) after being attached to substrates such as fiber products in order to exhibit water and oil repellency. Heat treatment at high temperature requires high energy.

Also, fluoropolymers are expensive.

Therefore, it is desirable to eliminate or reduce the amount of fluoropolymer.

Japanese Patent Laid-Open No. 2006-328624 discloses a water-repellent agent containing a non-fluorine-based polymer containing (meth)acrylate having 12 or more carbon atoms in the ester portion as a monomer unit , The constituent ratio of (meth)acrylate is 80-100 mass % with respect to the monomer unit total amount which comprises a fluorine-free polymer.

However, this water repellent was poor in water and oil repellency.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2006-328624

Contents of the invention

The problem to be solved by the invention

An object of the present invention is to provide a surface treatment agent which imparts excellent water and oil repellency and preferably does not use a fluorine-containing monomer, especially a fluorinated alkyl-containing monomer.

means to solve the problem

The present invention relates to an aqueous emulsion treatment agent, which contains:

(1) a polymer having a repeating unit derived from (i) a long-chain (meth)acrylate monomer and a repeating unit derived from (ii) a (meth)acrylate monomer having a cyclic hydrocarbon group;

(2) Surfactants; and

(3) Liquid medium containing water.

Preferred embodiments of the invention are as follows.

[1] A surface treatment agent which is an aqueous emulsion comprising:

(1) Non-fluoropolymers having the formula derived from (i): CH ₂ =CA ¹¹ -C(=O)-O—A ¹² [wherein, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a carbon A straight-chain or branched aliphatic hydrocarbon group with 18-30 atoms. ] a repeating unit of a long-chain (meth)acrylate monomer and a repeating unit derived from (ii) a (meth)acrylate monomer having a cyclic hydrocarbon group;

(2) Surfactants containing one or both of nonionic surfactants and cationic surfactants; and

(3) Liquid medium containing water.

[2] The surface treatment agent as described in [1], wherein the acrylate monomer (ii) having a cyclic hydrocarbon group has the formula: CH ₂ =CA ²¹ -C(=O)-OA ²² [where , A ²¹ is a hydrogen atom or a methyl group, and A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ] Compounds shown.

[3] The surface treating agent according to [1] or [2], wherein the surfactant (2) contains both a nonionic surfactant and a cationic surfactant, and the amount of the cationic surfactant is relatively The total amount of the nonionic surfactant and the cationic surfactant is 22% by weight or more.

[4] The surface treatment agent according to any one of [1] to [3], wherein

The nonionic surfactant is at least one selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides,

The cationic surfactant is at least one selected from the group consisting of amines, amine salts, quaternary ammonium salts, imidazolines, and imidazolinium salts.

[5] The surface treating agent according to any one of [1] to [4]4, wherein the surfactant contains a surface active compound having both an amide group and an amino group.

[6] The surface treatment agent according to any one of [1] to [5], wherein the surface treatment agent does not contain a fluoropolymer.

[7] The surface treatment agent according to any one of [1] to [5], wherein the surface treatment agent contains a fluoropolymer.

[8] The surface treatment agent according to any one of [1] to [7], wherein the surface treatment agent is a water and oil repellent or an antifouling agent.

[9] A method of treating a fiber product, comprising the step of treating the fiber product with the surface treatment agent described in any one of [1] to [8].

[10] A fiber product treated with the surface treatment agent according to any one of [1] to [8].

Invention effect

The surface treatment agent of the present invention does not use a fluoroalkyl-containing monomer, so there is no concern that fluorine-containing compounds will accumulate in the environment. The surface treatment agent of the present invention can impart excellent water and oil repellency, especially strong water repellency, to a substrate. In addition, water and oil repellency can be expressed by low temperature treatment without heat treatment at high temperature.

The treatment agent of the present invention has good stability (emulsion stability). The treatment agent of the present invention is excellent in strong water repellency typified by heavy rain.

Utilize the treatment agent that only contains non-fluorine polymer as active ingredient, can obtain the performance equal to or more than that of the treatment agent that only contains fluorine-containing alkyl-containing monomer as structural unit fluoropolymer as active ingredient (especially It is water-repellent and oil-repellent including initial water-repellent and oil-repellent).

detailed description

In the present invention, the copolymer (preferably non-fluoropolymer) has:

repeating units derived from (i) long chain (meth)acrylate monomers; and

A repeating unit derived from (ii) a (meth)acrylate monomer having a cyclic hydrocarbon group.

The copolymer may have one or both of (iii) a repeating unit derived from a short-chain (meth)acrylate monomer and a repeating unit derived from (iv) a non-fluorinated crosslinkable monomer.

The copolymer may contain fluorine atoms, but preferably does not contain fluorine atoms. That is, the copolymer is preferably a non-fluoropolymer.

(i) Long chain (meth)acrylate monomer

The long-chain (meth)acrylate monomer is a compound represented by the formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹² .

[wherein, A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is a straight-chain or branched aliphatic hydrocarbon group with 18 to 30 carbon atoms. ]

The long-chain (meth)acrylate monomer does not have a fluoroalkyl group. The long-chain (meth)acrylate monomer may contain fluorine atoms, but preferably does not contain fluorine atoms.

A ¹¹ is particularly preferably methyl.

A ¹² is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group. The linear or branched hydrocarbon group has 18-30 carbon atoms. The linear or branched hydrocarbon group preferably has 18 to 28 carbon atoms, particularly preferably 8 or 22, and is usually preferably a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group.

Particularly preferable specific examples of long-chain (meth)acrylate monomers are stearyl (meth)acrylate and behenyl (meth)acrylate. Particular preference is given to stearyl (meth)acrylate.

By the presence of long-chain (meth)acrylate monomers, the water and oil repellency imparted by the polymer increases.

(ii) Acrylate monomers having a cyclic hydrocarbon group

The acrylate monomer having a cyclic hydrocarbon group is preferably a compound represented by the formula: CH ₂ ═CA ²¹ —C(═O)—OA ²² .

[In the formula, ^A21 is a hydrogen atom or a methyl group, and ^A22 is a group containing a cyclic hydrocarbon with 4 to 30 carbon atoms. ]

The acrylate monomer having a cyclic hydrocarbon group is a monomer whose homopolymer has a high glass transition temperature (for example, 50° C. or higher, particularly 80° C. or higher).

The acrylate monomer having a cyclic hydrocarbon group does not have a fluoroalkyl group. The acrylate monomer having a cyclic hydrocarbon group may contain a fluorine atom, but preferably does not contain a fluorine atom.

A ²¹ is particularly preferably methyl.

^A22 is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, bridged ring groups, and the like. The cyclic hydrocarbon group is preferably saturated. The number of carbon atoms in the cyclic hydrocarbon group is 4-30, preferably 6-20. Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 20 carbon atoms, especially 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and aromatic aliphatic groups having 7 to 20 carbon atoms. group. The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include cyclohexyl, tert-butylcyclohexyl, isobornyl, dicyclopentyl, dicyclopentenyl, and adamantyl.

Specific examples of acrylate monomers having a cyclic hydrocarbon group include: cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, base) acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate Acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc.

The presence of the acrylate monomer having a cyclic hydrocarbon group improves the water repellency and oil repellency imparted by the copolymer.

(iii) Short-chain (meth)acrylate monomers

The copolymer may have repeat units derived from short chain (meth)acrylate monomers.

The short-chain (meth)acrylate monomer is preferably a compound represented by the formula: CH ₂ =CA ³¹ -C(=O)-OA ³² .

[wherein, A ³¹ is a hydrogen atom or a methyl group, and A ³² is a linear or branched aliphatic hydrocarbon group with less than 18 carbon atoms. ]

The short-chain (meth)acrylate monomer does not have a fluoroalkyl group. The short-chain (meth)acrylate monomer may contain fluorine atoms, but preferably does not contain fluorine atoms.

A ³¹ is particularly preferably methyl.

^A32 is a linear or branched hydrocarbon group. The linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group. The linear or branched hydrocarbon group has 1-17 carbon atoms. The linear or branched hydrocarbon group preferably has 1 to 14 carbon atoms, and is usually a saturated aliphatic hydrocarbon group, especially an alkyl group.

Specific examples of short-chain (meth)acrylate monomers are meth (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate ester, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate. Particularly preferable specific examples of short-chain (meth)acrylate monomers are lauryl (meth)acrylate and cetyl (meth)acrylate.

By the presence of a short-chain (meth)acrylate monomer, the water repellency and texture imparted by the polymer become better.

(iv) Non-fluorinated cross-linking monomer

The copolymer may or may not have a repeating unit derived from a non-fluorinated crosslinkable monomer.

A fluorine-free cross-linking monomer is a monomer not containing a fluorine atom. The non-fluorinated cross-linking monomer is a compound which has at least two reactive groups and/or ethylenic carbon-carbon double bonds (preferably (meth)acrylate groups), and does not contain fluorine. The non-fluorine cross-linking monomer can be a compound with at least 2 ethylenic carbon-carbon double bonds (preferably (meth)acrylate group), or have at least 1 ethylenic carbon-carbon double bond and at least 1 Compounds with reactive groups. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl and the like.

The non-fluorine cross-linking monomer may be mono(meth)acrylate, di(meth)acrylate or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorinated cross-linkable monomer may be di(meth)acrylate.

An example of a non-fluorine crosslinkable monomer is a vinyl monomer having a hydroxyl group.

Examples of non-fluorinated cross-linking monomers include: diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylamide ) acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, mono Vinyl chloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., but It is not limited to these.

The washing durability imparted by the polymer is improved by the presence of the non-fluorinated cross-linkable monomer.

(v) Other monomers

As other monomers (v) other than the monomers (i) to (iv), for example, non-fluorine non-crosslinkable monomers can be used.

Examples of other monomers include, for example: ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (methyl ) acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers. Other monomers are not limited to these examples.

Other monomers may be (preferably free of fluorine atoms) halogenated olefins.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably a olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferable specific examples of halogenated olefins include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide; and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

Since the water repellency is high, each monomer is preferably an acrylate.

Monomers (i) to (v) may be used alone or in combination of two or more.

The amount of the monomer (i) is at least 40% by weight, preferably at least 50 parts by weight, based on the copolymer. The amount of the monomer (i) may be 95 parts by weight or less, for example, 80 parts by weight or less, or 75 parts by weight or less, or 70 parts by weight or less with respect to the copolymer.

In the copolymer, with respect to 100 parts by weight of the monomer (i),

The amount of repeating unit (ii) can be 1 to 150 parts by weight, preferably 1 to 30 parts by weight,

The amount of repeating unit (iii) can be 0 to 100 parts by weight, preferably 1 to 30 parts by weight,

The amount of repeating unit (iv) can be 0 to 50 parts by weight, preferably 1 to 10 parts by weight,

The amount of the repeating unit (v) may be 0 to 100 parts by weight, preferably 1 to 30 parts by weight.

The number average molecular weight (Mn) of the copolymer is usually 1,000 to 1,000,000, for example, 5,000 to 500,000, particularly 3,000 to 200,000. The number average molecular weight (Mn) of the copolymer is usually determined by GPC (Gel Permeation Chromatography).

The polymer may be one kind of polymer or a combination of two or more kinds of polymers.

In the present invention, by copolymerizing monomers, a treatment agent composition in which a copolymer is dispersed or dissolved in a medium is obtained.

The monomers used in the present invention can be as follows:

Monomer (i)+(ii),

Monomer (i)+(ii)+(iii),

monomer (i)+(ii)+(iv), or

Monomer (i)+(ii)+(iii)+(iv).

In addition to this, monomers (v) can also be used.

It is preferable to use a non-fluorine crosslinkable monomer (iv). The monomer is preferably a combination of monomer (i)+monomer (ii)+monomer (iv) or a combination of monomer (i)+monomer (ii)+monomer (iv)+halogenated olefin. In this combination, the water-repellent property has high washing durability.

(2) Surfactant

In the processing agent of this invention, a surfactant contains a nonionic surfactant and a cationic surfactant. The surfactant may consist only of nonionic surfactants and cationic surfactants, or may contain other surfactants (other than nonionic surfactants and cationic surfactants). Examples of other surfactants are amphoteric surfactants. The surfactant is preferably free of anionic anionic surfactants.

(2-1) Non-ionic surfactants

Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.

Examples of ethers are compounds having an oxyalkylene group, preferably a polyoxyethylene group.

Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

An example of ester ether is a compound obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1 to 6 valent (especially 2 to 5 valent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

The polyhydric alcohol may be a 2- to 5-membered alcohol having 3 to 30 carbon atoms.

The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably a tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2-10. It is preferable that the number of the oxyalkylene groups in the molecule of a nonionic surfactant is 2-100 normally.

The nonionic surfactant is selected from ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, preferably nonionic surfactants having an oxyalkylene group.

Nonionic surfactants can be linear and/or branched aliphatic (saturated and/or unsaturated) groups of alkylene oxide adducts, linear and/or branched fatty acids (saturated and/or unsaturated) polyalkylene glycol esters, polyoxyethylene (POE)/polyoxypropylene (POP) copolymers (random copolymers or block copolymers), acetylene glycols Alkylene oxide adducts, etc. Among them, the structure of the alkylene oxide addition part and the polyalkylene glycol part is preferably polyoxyethylene (POE), polyoxypropylene (POP) or POE/POP copolymer (which can be a random copolymer , can also be a block copolymer) substance.

In addition, from the viewpoint of environmental problems (biodegradability, environmental hormones (environmental hormones), etc.), the nonionic surfactant preferably has no aromatic group structure.

The nonionic surfactant can be a compound represented by the formula: R ¹ O—(CH ₂ CH ₂ O) _p— (R ² O) _q —R ³ .

[wherein, R ¹ is an alkyl group with 1 to 22 carbon atoms or an alkenyl or acyl group with 2 to 22 carbon atoms, R ² are independently, the same or different, and are 3 or more carbon atoms (such as 3 to 10) ^R3 is a hydrogen atom, an alkyl group with 1 to 22 carbon atoms or an alkenyl group with 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more. ]

R ¹ preferably has 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms. Preferable specific examples of R ¹ include lauryl, tridecyl, and oleyl.

Examples of R ² are propylene, butylene.

In nonionic surfactants, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ² O) _q - may form a polyoxyalkylene chain.

The nonionic surfactant can be a polyoxyethylene alkylene alkyl group containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially a polyoxyalkylene chain) in the center. ether. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, among which an oxypropylene chain is preferable.

A preferred nonionic surfactant is a surfactant represented by the formula: R ¹ O—(CH ₂ CH ₂ O) _p —H.

[In the formula, R ¹ and p have the same meaning as above. ]

Specific examples of nonionic surfactants are:

C ₁₀ H ₂₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₆ H ₃₁

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

iso-C ₁₃ H ₂₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₀ H ₂₁ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅ and so on.

[In the formula, p and q have the same meaning as above. ]

Specific examples of nonionic surfactants include: ethylene oxide and hexylphenol, isooctylphenol, cetyl alcohol, oleic acid, alkane (C ₁₂ -C ₁₆ ) mercaptan, sorbitan monofatty acid ( Condensation products such as C ₇ -C ₁₉ ) or alkyl (C ₁₂ -C ₁₈ ) amines.

The ratio of the polyoxyethylene block to the molecular weight of the nonionic surfactant (copolymer) may be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight.

The average molecular weight of a nonionic surfactant is 300-5,000 normally, for example, it is 500-3,000.

A nonionic surfactant may be used individually by 1 type, and may use 2 or more types together.

The nonionic surfactant is preferably a combination of two or more. In the combination of two or more types, at least one nonionic surfactant can be R ¹ group (and/or R ³ group) R ¹ O—( A compound represented by CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [especially R ¹ O -(CH ₂ CH ₂ O) _p -H]. The amount of the nonionic surfactant whose R group is ^a branched alkyl group is 5 to 100 parts by weight, for example, 8 to 50 parts by weight, particularly 10 parts by weight, relative to 100 parts by weight of the total nonionic surfactant (B2). ~40 parts by weight. In the combination of two or more, the rest of the nonionic surfactants can be that the R ¹ group (and/or R ³ group) is a (saturated and/or unsaturated) straight-chain alkyl group (such as lauryl (n-lauric) group)) R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [particularly R ¹ O-(CH ₂ CH ₂ O) _p -H] compounds.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, Polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkyl alcohol amide, alkyl alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol poly Propylene glycol block copolymer, etc.

Since the dynamic surface tension of the water-based emulsion is reduced (that is, the water-based emulsion is easy to penetrate the substrate), it is preferred as a non-ionic surfactant to use acetylenic alcohols (especially acetylenic diols) or ethylene oxides of acetylenic alcohols (especially acetylenic diols). Base adducts.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both the alcohol and the alkylene oxide adduct are referred to as "alkynol compounds"). Particularly preferred nonionic surfactants are alkylene oxide adducts of monoalcohols or polyalcohols having unsaturated triple bonds.

The acetylenic alcohol compound is a compound containing one or more triple bonds and one or more hydroxyl groups. The acetylenic alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of polyoxyalkylene moieties include polyoxyethylene, polyoxypropylene, random addition structures of polyoxyethylene and polyoxypropylene, polyoxyethylene and polyoxypropylene Block addition structure of propylene.

Alkynol compounds can be of the formula:

HO－CR ¹¹ R ¹² －C≡C－CR ¹³ R ¹⁴ －OH, or

A compound represented by HO-CR ¹⁵ R ¹⁶ -C≡C-H.

[In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently, the same or different, and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]

The acetylenic alcohol compound may be an alkylene oxide adduct of the compound represented by the chemical formula. The alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group etc. are mentioned. In addition, examples of the alkylene oxide include alkylene oxides having 1 to 20 (especially 2 to 5) carbon atoms such as ethylene oxide and propylene oxide, and the addition number of the alkylene oxide is preferably 1 to 50.

Specific examples of acetylene alcohol compounds include acetylene diol, propynyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne -3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3 -Methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol Wait. Also mentioned are polyethoxylates and ethylene oxide adducts of the compounds of these specific examples.

A nonionic surfactant may not have a triple bond, or may have a triple bond. The non-ionic surfactant can be only one of the non-ionic surfactant without triple bond or the non-ionic surfactant with triple bond, or it can be the non-ionic surfactant without triple bond and the non-ionic surfactant with triple bond. Combination of triple bonded nonionic surfactants. In the combination of a nonionic surfactant not having a triple bond and a nonionic surfactant having a triple bond, the nonionic surfactant not having a triple bond (such as a nonionic surfactant having an oxyalkylene group) active agent) to the non-ionic surfactant with triple bond (such as acetylenic alcohol compound) can be 10:90-90:10, for example, 20:80-80:20.

(2－2) Cationic surfactant

The cationic surfactant is preferably a compound not having an amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazoline and imidazolinium salts.

Cationic surfactants are preferably amine salts, quaternary ammonium salts, and oxyethylene addition type ammonium salts. Specific examples of cationic surfactants are not particularly limited, and include: amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; alkyltrimethylammonium salts quaternary ammonium salt type surfactants such as , dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, and the like.

Examples of cationic surfactants are compounds of R ²¹ -N ⁺ (-R ²² )(-R ²³ )(-R ²⁴ )X ^- .

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently identical or different, and are hydrogen atoms or hydrocarbon groups with 1 to 50 carbon atoms, and X is an anionic group. ]

The hydrocarbon group may have an oxygen atom, and may be, for example, an oxyalkylene group such as a polyoxyalkylene group (the number of carbon atoms in the alkylene group is, for example, 2 to 5). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably hydrocarbon groups having 1 to 30 carbon atoms (such as aliphatic hydrocarbons, aromatic hydrocarbons or aromatic aliphatic hydrocarbons).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ are alkyl (such as methyl, butyl, stearyl, palmityl), aryl (such as phenyl), aralkyl (such as benzyl ( phenylmethyl), phenethyl (phenylethyl)).

Specific examples of X are halogens (such as chlorine), acids (such as inorganic acids such as hydrochloric acid, organic acids such as acetic acid (especially fatty acids)).

The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (the number of carbon atoms in the alkyl group is 4 to 30).

Cationic surfactants are preferably ammonium salts, particularly preferably quaternary ammonium salts. The cationic surfactant can be an ammonium salt represented by the formula: R ³¹ _p -N ⁺ R ³² _q X ^- .

[wherein, R ³¹ are independently independent, may be the same or different, and are linear and/or branched aliphatic (saturated and/or unsaturated) groups of C12 or more (for example, C ₁₂ to C ₅₀ ),

R ³² are independently independent and can be the same or different, and are H or C1-4 alkyl, benzyl, polyoxyethylene (the number of oxyethylene groups is, for example, 1 (especially 2, more particularly 3) to 50) ( Particular preference is given to CH ₃ , C ₂ H ₅ ),

X is a halogen atom (such as chlorine and bromine), C ₁ ~ C ₄ fatty acid base,

p is 1 or 2, q is 2 or 3, and p+q=4. ]

The number of carbon atoms of R ³¹ is 12-50, for example, 12-30.

Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, cetyltrimethylammonium bromide, trimethyloctadecyl Ammonium, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride , Benzyl dodecyl di(hydrogen polyoxyethylene) ammonium chloride.

Examples of amphoteric surfactants include alanines, imidazoline betaines, amide betaines, and acetate betaines. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethyl glycine betaine, fatty amidopropyl dimethyl glycine betaine, etc.

The surfactant may or may not contain a surface-active compound having an amide group and an amino group, ie, an amide-amine surfactant.

The amide-amine surfactant is preferably a compound represented by the formula: R ¹¹ -C(=O)(R ¹² -)N-(CH ₂ ) _n -N(-R ¹³ )(-R ¹⁴ ).

[In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are independently, the same or different, and are hydrogen atoms or hydrocarbon groups with 1-30 carbon atoms, and n is 0-10. ]

R ¹¹ is preferably alkyl or alkenyl. The number of carbon atoms of R ¹¹ may be 8-30, for example, 12-24. R ¹² , R ¹³ and R ¹⁴ are preferably a hydrogen atom or an alkyl group. The number of carbon atoms of R ¹² , R ¹³ and R ¹⁴ is preferably 1-6, particularly preferably 1-4. n is 0-10, for example, 1-10, especially 2-5.

Specific examples of amide-amine surfactants include isostearic acid diethylaminoacetamide, oleic acid dimethylaminoacetamide, oleic acid dimethylaminoacetamide, oleic acid diethylaminoacetamide , Diethylaminopropionamide Oleate, Diethylaminoacetamide Stearate, Diethylaminoacetamide Stearate, Dibutylaminoacetamide Stearate, Dibutylaminoacetamide Stearate, Dipropylaminopropionamide Stearate, Dipropylaminoacetamide Stearate, Dimethylaminoacetamide Stearate, Dimethylaminoacetamide Stearate, Diethylaminoacetamide Palmitate, Diethylaminopropionamide Palmitate, Dimethylaminoacetamide Palmitate, Dimethylaminopropionamide Palmitate, Diethylaminoacetamide Behenate, Diethylaminoacetamide Behenate, Behenic acid dimethylaminopropionamide, etc.

The amido-amine surfactants may be salts, for example acid salts or quaternary ammonium salts. In the salt, the cationic group is the nitrogen atom of the amino group, and the anionic group is various. Examples of the anionic group include halide ions, sulfate ions, carboxylate ions with 1 to 4 carbon atoms which may be substituted with hydroxyl groups, or alkylsulfate ions with 1 to 4 carbon atoms.

Acid salts are obtained by neutralizing amido-amines with acids, eg mineral and/or organic acids. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid. Examples of organic acids include short-chain monocarboxylic acids such as acetic acid and propionic acid; long-chain monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and erucic acid; Acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and other dicarboxylic acids; glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, citric acid and other hydroxy Carboxylic acid; polycarboxylic acid such as polyglutamic acid; acidic amino acid such as glutamic acid and aspartic acid; alkyl sulfate, alkyl sulfonate, alkyl phosphate, etc. Among these, inorganic acids, short-chain monocarboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, acidic amino acids are generally used, and, in particular, hydrochloric acid, sulfuric acid, acetic acid, succinic acid, glycolic acid, lactic acid, malic acid, lemon acid, glutamic acid.

Quaternary ammonium salts can be obtained by quaternizing amides-amines.

The amidoamine surfactant may be nonionic or ionic (cationic), preferably nonionic. In the case of nonionic, it is preferable to add and ionize an ionic compound such as an acid to use.

Nonionic surfactants, cationic surfactants, and amphoteric surfactants may each be one type or a combination of two or more.

The amount of the cationic surfactant is preferably 15% by weight or more, more preferably 20% by weight or more, particularly preferably 22% by weight or more, for example, with respect to the total amount of the nonionic surfactant and the cationic surfactant. 25% by weight or more, especially 30% by weight or more, more particularly 35% by weight or more. The upper limit of the amount of cationic surfactant is, for example, 60% by weight, especially 50% by weight. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 85:15 to 20:80, more preferably 80:20 to 40:60. The amount of other surfactants other than the nonionic surfactant and the cationic surfactant is 50% by weight or less, for example, 20% by weight or less, and may be 0.1% by weight or more based on the total amount of surfactants.

The quantity of cationic surfactant can be 0.05-10 weight part with respect to 100 weight part of polymers, for example, it may be 0.1-8 weight part. The total amount of surfactants may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, relative to 100 parts by weight of the polymer.

The amount of the amide-amine surfactant may be 80% by weight or less, for example, 5 to 70% by weight, particularly 10 to 60% by weight, based on the total amount of surfactants.

(3) Liquid medium

The liquid medium may be water alone or a mixture of water and (water-miscible) organic solvents. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% or more) with respect to the liquid medium. The liquid medium is preferably water alone.

The water and oil repellent composition of the present invention may contain only the above-mentioned non-fluoropolymer as the polymer (active ingredient), or may contain a fluorine-containing polymer in addition to the above-mentioned non-fluoropolymer. Usually, in a water and oil repellent composition (especially an aqueous emulsion), particles made of a non-fluoropolymer and particles made of a fluoropolymer exist separately. That is, it is preferable to mix the non-fluoropolymer and the fluoropolymer after producing the non-fluoropolymer and the fluoropolymer separately. Usually, it is preferable to mix the non-fluoropolymer emulsion and the fluoropolymer emulsion after separately producing the non-fluoropolymer emulsion (particularly aqueous emulsion) and the fluoropolymer emulsion (particularly aqueous emulsion).

Fluoropolymers are polymers having repeat units derived from fluoromonomers. The fluorine-containing monomer is preferably acrylate or acrylamide represented by the following general formula (I).

CH ₂ =C(-X)-C(=O)-Y-Z-Rf(I)

[wherein, X is a hydrogen atom, a linear or branched alkyl group with 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² base (wherein, X ¹ and X2 is a ^hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group with 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, Substituted or unsubstituted phenyl;

Y is -O- or -NH-;

Z is an aliphatic group with 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group with 6 to 18 carbon atoms, a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (wherein, R ¹ is an alkyl group with 1 to 4 carbon atoms), -CH ₂ CH(OZ ¹ )CH ₂ - group (wherein, Z ¹ is a hydrogen atom or acetyl group), -(CH ₂ ) _m -SO ₂ -( CH ₂ ) _n -group or -(CH ₂ ) _m -S-(CH ₂ ) _n -group (where m is 1 to 10 and n is 0 to 10);

Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]

The number of carbon atoms of the Rf group is preferably 1-6, particularly 4-6.

The fluorine-containing polymer may have repeating units derived from at least one non-fluorine monomer selected from the group consisting of halogenated olefin monomers, non-fluorine non-crosslinkable monomers, and non-fluorine crosslinkable monomers.

The halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. Specific examples of halogenated olefin monomers include vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide; and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

A preferred non-fluorine non-crosslinking monomer is a compound represented by the formula: CH ₂ =CA-T.

[wherein, A is a hydrogen atom, a methyl group or a halogen atom other than a fluorine atom (such as a chlorine atom, a bromine atom and an iodine atom),

T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 20 carbon atoms, or a chain or cyclic organic group having 1 to 20 carbon atoms having an ester bond. ]

Specific examples of non-fluorine non-crosslinking monomers include: alkyl (meth)acrylate, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (methyl) ) acrylates, methoxypolyethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers.

The non-fluorinated cross-linking monomer can be a compound with at least 2 carbon-carbon double bonds (such as (meth)propenyl), or a compound with at least 1 carbon-carbon double bond and at least 1 reactive group .

The weight ratio of the non-fluoropolymer to the fluoropolymer in the water and oil repellent composition can be 100:0~10:90, for example 90:10~20:80, preferably 80:20~30:70 .

The non-fluorine polymer and the fluorine-containing polymer may each be one type of polymer, or may be a combination of two or more types of polymers.

When using a combination of a non-fluorinated polymer and a fluorinated polymer, performance (especially water and oil repellency) equal to or higher than when only a fluorinated polymer is used can be obtained.

The polymers (non-fluorine polymers and fluorine-containing polymers) in the present invention can be produced by any usual polymerization method, and the conditions of the polymerization reaction can also be selected arbitrarily. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization are mentioned. Emulsion polymerization is preferred.

If the treatment agent of the present invention is an aqueous emulsion, the method for producing the polymer is not limited. For example, a polymer can be produced by solution polymerization, and then the solvent can be removed, and a surfactant and water can be added to obtain an aqueous emulsion.

In solution polymerization, the method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, nitrogen substitution, and heating and stirring in the range of 30-120 degreeC for 1-10 hours is employ|adopted. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, peroxypivalic acid tert-butyl ester, diisopropyl peroxydicarbonate, etc. A polymerization initiator can be used in the range of 0.01-20 weight part with respect to 100 weight part of monomers, for example, the range of 0.01-10 weight part.

The organic solvent is a solvent that is inactive and capable of dissolving the monomers, such as esters (such as esters with 2 to 30 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (such as carbon atoms Ketones with 2 to 30 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (such as alcohols with 1 to 30 carbon atoms, specifically isopropanol). Specific examples of organic solvents include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4 -Dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane alkanes, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. The organic solvent can be used in the range of 10 to 2000 parts by weight, for example, in the range of 50 to 1000 parts by weight with respect to 100 parts by weight in total of the monomers.

In the emulsion polymerization, monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen replacement, they are stirred for 1 to 10 hours in the range of 50 to 80° C. to copolymerize. The polymerization initiator can use benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisiso Butylamidine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and other water-soluble initiators or azobisisobutyronitrile, benzoyl peroxide, ditertiary Oil-soluble initiators such as butyl peroxide, lauryl peroxide, cumyl hydroperoxide, tert-butyl peroxypivalate, and diisopropyl peroxydicarbonate. A polymerization initiator can be used in the range of 0.01-10 weight part with respect to 100 weight part of monomers.

In order to obtain an aqueous copolymer dispersion excellent in standing stability, it is preferable to use an emulsification device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer to micronize and polymerize monomers in water. Moreover, as an emulsifier, various emulsifiers of anionic type, cationic type, or nonionic type can be used, and can be used in the range of 0.5-20 weight part with respect to 100 weight part of monomers. Preference is given to using anionic and/or nonionic and/or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizing agent that makes these monomers fully compatible, for example, add a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, emulsifiability and copolymerizability can be improved.

As the water-soluble organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc. can be cited, relative to 100 parts by weight of water, it can be in the range of 1 to It is used in the range of 50 parts by weight, for example, in the range of 10 to 40 parts by weight. In addition, examples of low-molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, etc., based on 100 parts by weight of the total amount of monomers , can be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

Chain transfer agents can be used in the polymerization. The molecular weight of the copolymer can be varied according to the amount of the chain transfer agent used. Examples of chain transfer agents are thiol group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially (for example, alkyl mercaptans with 1 to 30 carbon atoms)), sodium hypophosphite, hydrogen sulfite, etc. Inorganic salts such as sodium, etc. The chain transfer agent can be used in the range of 0.01 to 10 parts by weight, for example, in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of monomers.

The treatment agent composition of the present invention may be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The treatment agent composition contains a copolymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight relative to the treatment agent composition.

In the treatment agent composition, the concentration of the copolymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

The treating agent composition of the present invention can be applied to a treated object by a conventionally known method. Usually, the treatment agent composition is dispersed in an organic solvent or water, diluted, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, or bubble coating, and then dried. . In addition, it can be applied together with a suitable crosslinking agent (such as blocked isocyanate) for curing (curing) when required. It is also possible to add insect repellent, softener, antibacterial agent, flame retardant, antistatic agent, paint fixing agent, anti-wrinkle agent, etc. to the treatment agent composition of the present invention. The concentration of the copolymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (particularly during dip coating), for example, 0.05 to 10% by weight.

As the object to be treated with the treatment agent composition (such as water and oil repellent) of the present invention, fiber products, stone materials, filters (such as electrostatic filters), dust masks, parts of fuel cells (such as gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramics, plastics, coated surfaces and plaster, etc. Various examples can be given as fiber products. Examples include natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, rayon, and acetate fibers. Semi-synthetic fibers such as glass fibers, carbon fibers, asbestos fibers and other inorganic fibers, or their mixed fibers.

The fiber product may be in any form such as fiber or cloth.

The treatment composition of the present invention can be used as an internal release agent or an external release agent.

The copolymer can be applied to a fibrous substrate (for example, a fibrous product, etc.) by any known method of treating a fibrous product with a liquid. When the fiber product is cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed onto the cloth. The treated fiber product is preferably dried, for example, heated at 100°C to 200°C in order to express oil repellency.

Alternatively the copolymer can be applied to fiber products by a laundering process, for example by laundering application or dry cleaning or the like.

The fibrous product to be treated is typically a cloth, which includes textiles, woven and non-woven fabrics, cloth in the form of clothing and blankets, but may also be fibres, threads or intermediate fibrous products (e.g. sliver or thick thread) Wait). Fiber product materials can be natural fibers (such as cotton or wool, etc.), chemical fibers (such as viscoserayon or lyocell, etc.) or synthetic fibers (such as polyester, polyamide or acrylic fibers, etc.) , or it can also be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers, etc.). The polymers of manufacture of the present invention are particularly effective in imparting oleophobicity and oil repellency to cellulosic fibers such as cotton or rayon and the like. Also, the methods of the present invention generally impart hydrophobicity and water repellency to fibrous articles.

Alternatively, the fibrous substrate may also be leather. In order to render the leather hydrophobic and oleophobic, the manufacturing polymers are applied to the leather from aqueous solutions or aqueous emulsions at various stages of leather processing, for example during wet processing of the leather or during the finishing of the leather.

Alternatively, the fibrous substrate may also be paper. The making polymer can be applied to the preformed paper, or it can be applied at various stages of paper making, such as during the drying of the paper.

The term "treatment" refers to applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the copolymer as an active ingredient of the treatment agent penetrates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.

The zeta potential of the aqueous emulsion treatment agent is preferably +30 mV or more. The zeta potential was measured by the laser Doppler method (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).

The dynamic surface tension of the aqueous emulsion treatment agent is preferably 55 mN/m or less. The dynamic surface tension was measured by the maximum bubble pressure method (BP-D5 manufactured by Kyowa Surface Science Co., Ltd.).

Example

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, these descriptions do not limit the present invention.

Hereinafter, unless otherwise specified, parts, %, or ratios represent parts by weight, % by weight, or ratio by weight.

The procedure of the test is described below.

Bundesmann water repellency test

According to the method described in JIS L1092 (C) (Bundesmann test), the water repellency was evaluated by raining under the conditions of 80 cc/min of rainfall, 20° C. of rainfall water temperature, and 5 minutes or 10 minutes of rainfall. The water repellency is represented by 6 grades (0, 50, 70, 80, 90 and 100) from 0 to 100. A higher score indicates better water repellency. Grades marked with + (-) indicate that they are slightly better (worse) in quality.

Manufacturing example 1

In a 500mL autoclave, add stearyl acrylate=45g, isobornyl methacrylate=5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxygen Ethylene (EO: 18) secondary alkyl (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 2

Add stearyl acrylate=40g, isobornyl methacrylate=10g, pure water=145g, tripropylene glycol=15g, acetylene glycol polyoxyethylene adduct=1g, Polyoxyethylene (EO: 18) isotridecyl ether = 2 g, dioctadecyl dimethyl ammonium chloride = 2 g, and was dispersed by ultrasonic emulsification at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer. Manufacturing example 3

In a 500mL autoclave, add stearyl acrylate=40g, adamantyl acrylate=10g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyethylene oxide Base (EO: 18) secondary alkyl (C12-14) ether = 2 g, dioctadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer. Manufacturing Example 4

Add stearyl acrylate = 30g, lauryl acrylate = 5g, benzyl methacrylate = 15g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate into a 500mL autoclave =1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, di-octadecyl dimethyl ammonium chloride = 1.5g, ultrasonic at 60°C under stirring Emulsify and disperse for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 5

Add stearyl acrylate = 25g, behenyl acrylate = 15g, isobornyl methacrylate = 10g, pure water = 145g, tripropylene glycol = 15g, sorbitan mono-oil in a 500mL autoclave Ester = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, dioctadecyldimethylammonium chloride = 1.5g, under stirring at 60°C Disperse by ultrasonic emulsification for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 6

Add stearyl acrylate = 35g, isobornyl methacrylate = 10g, glycidyl methacrylate = 5g, pure water = 145g, tripropylene glycol = 15g, acetylene glycol poly Oxyethylene adduct = 1g, polyoxyethylene (EO: 18) isotridecyl ether = 2g, di-octadecyldimethylammonium chloride = 2g, under stirring at 60°C Disperse by ultrasonic emulsification for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing example 7

Add stearyl acrylate = 37.5g, isobornyl methacrylate = 10g, hydroxyethyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, sorbose in a 500mL autoclave Alcohol anhydride monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, di-octadecyldimethylammonium chloride = 1.5g, stirring Disperse by ultrasonic emulsification at 60°C for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 8

In a 500mL autoclave, add stearyl acrylate=35g, benzyl methacrylate=10g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyoxyethylene Ethyl (EO: 18) secondary alkyl (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After nitrogen replacement in the autoclave, 5 g of vinyl chloride was added by pressing in, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and reacted at 60° C. for 3 hours to obtain Aqueous dispersions of polymers. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Manufacturing Example 9

Add stearyl acrylate = 25g, adamantyl acrylate = 15g, glycidyl methacrylate = 2.5g, pure water = 145g, tripropylene glycol = 15g, sorbitan mono Oleic acid ester=1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether=2g, di-octadecyl dimethyl ammonium chloride=1.5g, under stirring at 60 ℃ and use ultrasonic emulsification to disperse for 15 minutes. After nitrogen substitution in the autoclave, 7.5 g of vinylidene chloride was added by pressing in, 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60° C. for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer. Comparative Manufacturing Example 1

Add stearyl acrylate = 50g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) secondary alkane into a 500mL autoclave Base (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, and ultrasonically emulsify and disperse at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 2

Add stearyl acrylate = 40g, lauryl acrylate = 10g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleate = 1.5g, polyoxyethylene (EO: 18) Secondary alkyl (C12-14) ether = 2 g, di-octadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer. Comparative Manufacturing Example 3

In a 500mL autoclave, add stearyl acrylate=25g, behenyl acrylate=25g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, polyethylene oxide Base (EO: 18) secondary alkyl (C12-14) ether = 2 g, dioctadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer. Comparative Manufacturing Example 4

Add stearyl acrylate = 20g, lauryl acrylate = 25g, glycidyl methacrylate = 5g, pure water = 145g, tripropylene glycol = 15g, sorbitan monooleic acid in a 500mL autoclave Ester = 1.5g, polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether = 2g, di-octadecyldimethylammonium chloride = 1.5g, use at 60°C under stirring Ultrasonic emulsification and dispersion for 15 minutes. After substituting nitrogen in the autoclave, 2,2-azobis(2-amidinopropane) 2 hydrochloride=0.5 g was added, and it was made to react at 60 degreeC for 3 hours, and the aqueous dispersion liquid of the polymer was obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Comparative Manufacturing Example 5

In a 500mL autoclave, add stearyl acrylate=35g, glycidyl methacrylate=2.5g, pure water=145g, tripropylene glycol=15g, sorbitan monooleate=1.5g, poly Ethylene oxide (EO: 18) secondary alkyl (C12-14) ether = 2 g, dioctadecyl dimethyl ammonium chloride = 1.5 g, ultrasonic emulsification and dispersion at 60° C. for 15 minutes while stirring. After nitrogen substitution in the autoclave, 12.5 g of vinyl chloride was added by pressing, and 2,2-azobis(2-amidinopropane) 2 hydrochloride = 0.5 g was added, and the reaction was carried out at 60°C for 3 hours. An aqueous dispersion of the polymer is obtained. Further, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the resulting polymer is basically the same as that of the added monomer.

Table 1 shows raw materials used in Production Examples and Comparative Production Examples.

Reference Example 1 (Manufacture of Fluorine-based Removal Agent)

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (n=2.0) 14.9g, stearyl acrylate 43, 46g, pure water into a 500ml reaction flask 110g, dipropylene glycol monomethyl ether 18.62g, distearyl dimethyl ammonium chloride 3.08g, stearyl trimethyl ammonium chloride 0.87g, polyoxyethylene lauryl ether (EO: 18, EO represents the number of oxyethylene units) 2.1 g, and polyoxyethylene isotridecyl ether (EO: 3) 0.65 g were ultrasonically emulsified and dispersed at 60° C. for 15 minutes while stirring. After nitrogen replacement in the reaction flask, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride and 9 g of water was added, and the reaction was carried out at 60° C. for 5 hours. An aqueous dispersion of the polymer (fluorine-based repellant) was obtained. The composition of the polymer is basically the same as that of the added monomers.

Example 1

50 g of the aqueous liquid prepared in Production Example 1 was diluted with tap water to prepare a test liquid (1000 g). A cloth (510 mm×205 mm) was immersed in the test solution, passed through a mangle, and treated with a pin tenter at 160° C. for 2 minutes. The test cloth is submitted to the water repellency test. Repeat the same steps as above for PET taffeta and nylon taffeta. Then, perform the Bondis gate test. The results are shown in Table 2.

Embodiment 2～9 and comparative example 1～5

Treat in the same way as in Example 1, and carry out the Bondis gate test. The results are shown in Table 2.

Examples 10-11

Use tap water to dilute each aqueous liquid (non-fluorine-based dialing agent) 25g and the fluorine-based dialling agent 25g made in Reference Example 1 to prepare test solution (1000g) in the manufacture example 1 and 4, and embodiment 1 In the same way, the Bondis gate test was carried out. The results are shown in Table 2.

[Table 1]

Note)

Emulsifier 1: Sorbitan monooleate/polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether/dioctadecyldimethylammonium chloride=3/4/ 3 (weight ratio)

Emulsifier 2: Acetylene glycol polyoxyethylene adduct/polyoxyethylene (EO: 18) isotridecyl ether/di-octadecyldimethylammonium chloride=2/4/ 4 (weight ratio)

Industrial availability

The treating agent of the present invention is suitably applied to substrates such as fiber products and masonry, and imparts excellent water and oil repellency to the substrates.

Other aspects of the present invention are as follows.

<1> Water-based emulsion treatment agent, which contains:

(1) A polymer having the formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹² [wherein, A ¹¹ is hydrogen] derived from (i) in an amount of 40% by weight or more relative to the polymer atom or a methyl group, and A12 is a straight-chain or branched aliphatic hydrocarbon group with ¹⁸ to 30 carbon atoms. ] a repeating unit of a long-chain (meth)acrylate monomer shown in ], and a repeating unit derived from (ii) a (meth)acrylate monomer having a cyclic hydrocarbon group;

(2) Surfactants containing nonionic surfactants and cationic surfactants; and

(3) Liquid medium containing water.

<2> The aqueous emulsion treatment agent according to <1>, wherein the acrylate monomer (ii) having a cyclic hydrocarbon group is represented by the formula: CH ₂ =CA ²¹ -C(=O)-OA ²² compound of.

[In the formula, ^A21 is a hydrogen atom or a methyl group, and ^A22 is a group containing a cyclic hydrocarbon with 4 to 30 carbon atoms. ]

<3> The aqueous emulsion treatment agent according to <1> or <2>, wherein the polymer (1) further has a formula derived from (iii): CH ₂ =CA ³¹ -C(=O)-OA ³² is a repeating unit of a short-chain (meth)acrylate monomer.

[wherein, ^A21 is a hydrogen atom or a methyl group, and ^A32 is a linear or branched aliphatic hydrocarbon group with less than 18 carbon atoms. ]

<4> The aqueous emulsion treatment agent according to any one of <1> to <3>, wherein the polymer (1) further has a repeating unit derived from (iv) a non-fluorinated crosslinkable monomer.

<5> The aqueous emulsion treatment agent according to <4>, wherein the non-fluorinated crosslinkable monomer (iv) is a compound having at least two ethylenically unsaturated double bonds, or at least one ethylenically unsaturated double bond bond and at least one reactive group.

<6> The aqueous emulsion treatment agent according to any one of <1> to <5>, wherein the polymer (1) has (v) a repeating unit derived from a halogenated olefin monomer.

<7> The aqueous emulsion treatment agent according to <6>, wherein the (v) halogenated olefin monomer is at least one selected from vinyl chloride and vinylidene chloride.

<8> The aqueous emulsion treatment agent according to any one of <1> to <7>, wherein the polymer (1) does not contain a fluorine atom.

<9> The water-based emulsion treatment agent according to any one of <1> to <8>, wherein

In the polymer (1), the amount of the repeating unit (ii) is 1 to 150 parts by weight, the amount of the repeating unit (iii) is 0 to 100 parts by weight, and the repeating unit ( The amount of iv) is 0 to 100 parts by weight, and the amount of the repeating unit (v) is 0 to 100 parts by weight.

<10> The aqueous emulsion treatment agent according to any one of <1> to <9>, wherein the amount of the cationic surfactant is 15% by weight or more in the surfactant.

<11> The aqueous emulsion treatment agent according to any one of <1> to <10>, wherein the nonionic surfactant has the formula: R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) a compound represented by _q -R ³ .

[wherein, R ¹ is an alkyl group with 1 to 22 carbon atoms or an alkenyl or acyl group with 2 to 22 carbon atoms, R ² are independently, the same or different, and are 3 or more carbon atoms (such as 3 to 10) ^R3 is a hydrogen atom, an alkyl group with 1 to 22 carbon atoms or an alkenyl group with 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more. ]

<12> The aqueous emulsion treatment agent according to <11>, wherein the nonionic surfactant is an alkynyl alcohol compound selected from the group consisting of alkynyl alcohols and ethylene oxide adducts of alkynyl alcohols.

<13> The aqueous emulsion treatment agent according to <12>, wherein the acetylenic alcohol compound has the formula: HO-CR ¹¹ R ¹² -C≡C-CR ¹³ R ¹⁴ -OH or HO-CR ¹⁵ R ¹⁶ -C≡ Compounds represented by C-H.

[In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently, the same or different, and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. ]

<14> The aqueous emulsion treatment agent according to any one of <1> to <13>, wherein the cationic surfactant has the formula: R ²¹ -N ⁺ (-R ²² )(-R ²³ )(- R ²⁴ ) ^A compound represented by X-.

[In the formula, R ²¹ , R ²² , R ²³ and R ²⁴ are independently identical or different, and are hydrocarbon groups with 1 to 30 carbon atoms, and X is an anionic group. ]

<15> The aqueous emulsion treatment agent according to any one of <1> to <14>, wherein the fiber treatment agent further contains a fluoropolymer.

<16> The water-based emulsion treatment agent according to any one of <1> to <15>, wherein the water-based emulsion has a zeta potential of +30 mV or more.

<17> The water-based emulsion treatment agent according to any one of <1> to <16>, wherein the dynamic surface tension of the water-based emulsion is 55 mN/m or less.

<18> The aqueous emulsion treatment agent according to any one of <1> to <17>, which is a fiber treatment agent.

<19> The water-based emulsion treatment agent according to any one of <1> to <18>, which is a water and oil repellent or an antifouling agent.

<1> A method of treating a fiber product, including the step of treating the fiber product with the aqueous emulsion treatment agent according to any one of <1> to <19>.

<21> A fiber product treated with the aqueous emulsion treatment agent according to any one of <1> to <19>.

Claims (10)

1. a surface conditioning agent, it is water serial emulsion, and this surface conditioning agent is characterised by, contains:

(1) non-fluorinated polymer, it has and is derived from (i) formula: CH₂=CA¹¹-C (=O)-O-A¹²The repetitive of shown long-chain (methyl) acrylate monomer and be derived from the repetitive that (ii) has (methyl) acrylate monomer of cyclic hydrocarbon group, in formula, A¹¹For hydrogen atom or methyl, A¹²Aliphatic alkyl for the straight or branched of carbon number 18～30；

(2) surfactant containing nonionic surfactant and the one or both of cationic surface active agent；With

(3) moisture liquid medium.

2. surface conditioning agent as claimed in claim 1, it is characterised in that:

The acrylate monomer (ii) with cyclic hydrocarbon group is formula: CH₂=CA²¹-C (=O)-O-A²²Shown compound,

In formula, A²¹For hydrogen atom or methyl, A²²The group containing cyclic hydrocarbon for carbon number 4～30.

3. surface conditioning agent as claimed in claim 1 or 2, it is characterised in that:

Surfactant (2) containing nonionic surfactant and cationic surface active agent, the amount of cationic surface active agent relative to the total amount of nonionic surfactant and cationic surface active agent at more than 22 weight %.

4. the surface conditioning agent as according to any one of claims 1 to 3, it is characterised in that:

Nonionic surfactant is at least one in ether, ester, ester ether, alkanolamide, polyhydric alcohol and amine oxide,

Cationic surface active agent is at least one in amine, amine salt, quaternary ammonium salt, imidazoline and imidazoline salt.

5. the surface conditioning agent as according to any one of Claims 1 to 4, it is characterised in that:

Surfactant comprises the surface active cpd with amide groups and amino.

6. the surface conditioning agent as according to any one of Claims 1 to 5, it is characterised in that:

Surface conditioning agent does not contain fluoropolymer.

7. the surface conditioning agent as according to any one of Claims 1 to 5, it is characterised in that:

Surface conditioning agent contains fluoropolymer.

8. the surface conditioning agent as according to any one of claim 1～7, it is characterised in that:

Surface conditioning agent is water extraction oil extracticn agent or anti-fouling agent.

9. the method that fibre is processed, it is characterised in that:

Including step fibre processed with the surface conditioning agent according to any one of claim 1～8.

10. the fibre processed by the surface conditioning agent according to any one of claim 1～8.